AU649151B2 - Polyesters suitable for use in outdoor-durable coating systems - Google Patents
Polyesters suitable for use in outdoor-durable coating systems Download PDFInfo
- Publication number
- AU649151B2 AU649151B2 AU20462/92A AU2046292A AU649151B2 AU 649151 B2 AU649151 B2 AU 649151B2 AU 20462/92 A AU20462/92 A AU 20462/92A AU 2046292 A AU2046292 A AU 2046292A AU 649151 B2 AU649151 B2 AU 649151B2
- Authority
- AU
- Australia
- Prior art keywords
- acid
- polyester
- outdoor
- anhydride
- durable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 229920000728 polyester Polymers 0.000 title claims description 53
- 238000000576 coating method Methods 0.000 title claims description 28
- 239000011248 coating agent Substances 0.000 title claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- 239000008199 coating composition Substances 0.000 claims description 14
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 7
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims description 7
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 7
- 229940117969 neopentyl glycol Drugs 0.000 claims description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- -1 S 15 anhydrides Chemical class 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- 239000004645 polyester resin Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- XGJZQNMUVTZITK-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexamethoxy-1,3,5-triazine-2,4,6-triamine Chemical compound CON(OC)C1=NC(N(OC)OC)=NC(N(OC)OC)=N1 XGJZQNMUVTZITK-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- VYZKQGGPNIFCLD-UHFFFAOYSA-N 3,3-dimethylhexane-2,2-diol Chemical compound CCCC(C)(C)C(C)(O)O VYZKQGGPNIFCLD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 101150038956 cup-4 gene Proteins 0.000 description 1
- CWRUZINMWUIUOD-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid;cyclohexane-1,4-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1.OC(=O)C1CCCCC1C(O)=O CWRUZINMWUIUOD-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31794—Of cross-linked polyester
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Description
yR 9151 S F Ref: 216479
AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT
ORIGINAL
9* a *99 Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: DSM N.V.
Het Overloon 1 6411 TE Heerlen THE NETHERLANDS Gerard Hardeman, Wilhelmina Westerhof, Johannes Wilhelmus Besamusca Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Polyesters Suitaule for Use in Out or-Durable Coating Systems The following statement is a full description of Lthis invention, including the best method of performing it known to me/us:- 5845/5 1 Polyesters Suitable For Use In Outdoor-Durable Coating Systems The invention relates to polyesters for use in outdoor-durable coating systems such as, for instance, coil coating systems.
The use of polyesters in coil coating systems is disclosed in "Developments in Coil Coatings" in Polymers Paint Colour Journal (13 December 1989; Volume 179, No.
4251) by Gary Williams.
A disadvantage of the nowadays for outdoor-durable coil-coatings used siliconemodified polyesters (disclosed in said article) is their bad flexibility.
It is an object of the present invention to provide polyesters which result in coatings combining a good outdoor durability and good mechanical properties. Said combination makes them more suitable for outdoor-durable applications.
The polyester according to the invention is based on at least 50 moles 1,4-cyclohexane dicarboxylic acid and a hexahydrophthalic acid (anhydride) as acid components and the polyester has a molecular weight Mn between 2600 and 10000.
More preferably the molecular weight is above 3000.
These polyesters result in coil coating systems combining an excellent outdoor durability with good mechanical properties.
According to a first embodiment of the present invention there is provided r polyester for use in outdoor-durable coating systems, having a molecular weight Mn between 2,600 and 10,000, said polyester being substantially oil-free and resulting from the process comprising the steps of reacting an acid component comprising an acid and/or an acid anhydride, with a polyalcohol, wherein at least 50 mol of said acid component comprises 1,4-cyclohexane dicarboxylic acid and a hexahydrophthalic acid (anhydride).
25 According to a second embodiment of the present invention there is provided a S* coating composition based on the resin of the first embodiment.
According to a preferred embodiment of the invention the polyester is based on 55-100 moles 1,4-cyclohexane dicarboxylic acid and a hexahydrophthalic acid 3 (anhydride) as acid components.
S 30 The polyester can be a hydroxyl-functional polyester or a carboxyl-functional polyester. Preferably the polyester is a hydroxyl-functional polyester.
*ee oe.
1 of 2 (10) AE 7159 The polyester is a substantially oil-free polyester.
The polyesters according to the invention can be obtained by reacting an acid or an acid anhydride with a polyalcohol.
The molar ratio of polyalcohol to acid or acid anhydride is usually between 1.2:1.0 and 1.0:1.0 in case of an hydroxyl-functional polyester.
In addition to 1,4-cyclohexane dicarboxylic acid and a hexahydrophthalic acid (anhydride), the polyester can be based on a maximum of 50 moles other acid components such as, for instance, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, decanedicarboxylic acid and/or dimerized fatty acids or acid anhydrides such as, for instance, phthalic acid anhydride and succinic acid Sanhydride.
Suitable hexahydrophthalic acids or anhydrides include methylhexahydrophthalic acid, hexahydroisophthalic acid and/or hexahydrophthalic acid or anhydride.
According to a preferred embodiment of the invention the amount of aromatic acid units is lower than mol More preferably, the amount of aromatic acid units Sis substantially 0 mol Substantially aromatic acid free compositions result in coatings with an excellent gloss.
Suitable polyalcohols for the preparation of the hydroxyl-functional polyester include butanediol-(1,4), hexanediol-(1,6), neopentylglycol, trimethylpentanediol, hydroxypivalineneopentylglycol ester, tricyclodecanedimethanol, cyclohexanedimethanol and trimethylolpropane.
Preferably neopentylglycol and/or hydroxypivalineneopentylglycol ester are used.
Preferably the hydroxyl groups of the diol or polyol are attached to different carbon atoms which are not directly connected to each other. They are separated by at least one carbon atom.
(10) AE 7159 The ratio of cyclohexanedicarboxylic acid (CHDA) to hexahydrophthalic acid (anhydride) (HHPAA) and optionally other acid components can be chosen in dependence of the desired use. The molar ratio of 1,4-cyclohexanedicarboxylic acid hexahydrophthalic acid (anhydride) may range between, for instance, 5 1 and 1 A suitable polyester is, for example, based on CHDA and HHPAA as acid components in a molar ratio 1 1.
Another suitable polyester is based on, for example, 55 mol CHDA and HHPAA in a molar ratio 80 and 45 mol isophthalic acid.
It is possible to use mixtures of polyesters according to the invention to optimalize and to obtain certain characteristics of the coating.
The esterification reaction preferably takes place in a nitrogen atmosphere at temperatures of between 180°C and 260°C. As additives, catalysts such as, for instance, dibutyltin oxide, tin chloride or tetrabutoxytitanate and antioxidants such as, for instance, triphenylphosphite may be added. During the reaction, the reaction water released is removed by distillation and the desired degree of esterification is achieved by applying azeotropic distillation or vacuum in the final phase. The reaction results in a polyester which can subsequently be dissolved in an organic solvent or a mixture of solvents. Suitable solvents include aromatic hydrocarbons and glycol ether esters such as for example methylpropylene-glycolacetate or ethylpropyleneglycolacetate or glycol ethers such as butyl glycol.
The polyesters according to the invention do hardly absorb any UV-light and are because of this reason UV-resistant.
The coating composition can be obtained by first preparing a pigment paste in which the polyester resin according to the invention and pigment, for instance titanium dioxide, are mixed for example in a weight ratio of between 80 120 and 120 80, preferably in a weight ratio (10) AE 7159 of substantially virtually 1 1. Subsequently, after cooling to room temperature, crosslinkers such as for example an amino resin, for instance hexamethoxymelamine, or an isocyanate-functional hardener, for instance the biuret of 1,6 hexanediisocyanate (Desmodur NTM), can be added. Also a catalyst, for instance paratoluenesulphonic acid or dibutyltin dilaurate, can be added in amounts of preferably less than 2% (wt) (calculated on the coating composition).
Optionally, other additives such as for example flow modifiers and wetting agents may be used also.
The weight ratio polyester resin crosslinker is usually between 60 40 and 95 The composition can be diluted with solvents.
Suitable solvents include aromatic hydrocarbon fractions, for instance Solvesso 150
T
M (of Esso), methylpropyleneglycolacetate (MPA) or butyl glycol. In this way a coating composition with a solids content of between, for instance, S" 20 60% and 80% can be obtained.
The coating composition can be applied with a wire S.coater on special chromated alucoil with a dry coat thickness of 15 30 pm. The baking cycle is 45 50 seconds at 295 0 C, which corresponds with a peak metal temperature (PMT) of 232 0 C 241 0
C.
Preferably the coating composition according to the invention is used in the so-called outdoor-durable coil coatings. Other applications include, for instance, the use as an automotive top coating for plastic substrates.
The polyesters according to the invention can also be applied for water-borne coatings.
The invention will be further elucidated by the following examples without, however, being limited thereto.
(10) AE 7159 Examples Example I Preparation of a polyester resin 2.1 moles hydroxypivalineneopentylglycol ester (Esterdiol 204TM), 8.5 moles neopentylglycol (NPG), 4.7 moles 1,4-cyclohoxanedicarboxylic acid (CHDA), 5,3 moles hexahydrophthalic anhydride (HHPA) and 0.05 part by weight dibutyltin oxide were heated in a glass reaction flask with a mechanical stirrer, a thermometer and a distillation arrangement with vigreux, in a nitrogen atmosphere. The esterification reaction started at 180 0 C and the reaction water formed was removed by distillation. The maximum reaction temperature was 240 0 C. After the reaction mixture was clear, azeotropic distillation was started using an aromatic hydrocarbon fraction (Solvesso 150TM) until an acid number lower than 7 was reached.
S. The final acid number of the solid resin was S" 20 between 4 and 7. The viscosity measured as a 60% solution in Solvesso 150TM/butyl glycol in an Emila with spindle 100 at 23 0 C was 9.5-10.5 dPa.s.
The molecular weight M s was 4500 and the hydroxyl functionality Mn is determined by GPC (gel permeation chromatography; polystyrene standard).
Example II :Preparation of a polyester resin Example I was repeated using, instead of 8.5 moles NPG and 2.1 moles Esterdiol 204T, 6.8 moles NPG, 2.0 moles Esterdiol 204TM and 1.8 hexanediol-1,6. Further, instead of 4.7 moles CHDA and 5.3 moles HHPA, 4.35 moles CHDA, 1.15 moles HHPA and 4.50 moles IPA (isophthalic acid) were used.
The final acid number of the solid resin was between 4 and 7. The viscosity measured in an Emila with spindle 100 at 23 0 C was between 27 and 30 dPa.s.
The molecular weight (Mn) was 4500 and the hydroxyl-functionality (10) AE 7159 Example III Preparation of coating composition To 45.8 parts by weight of a hydroxyl-functional polyester resin obtained according to Example I (dissolved in Solvesso 150M and butyl glycol 27.50 parts by weight solid), 50.0 parts by weight titanium dioxide (Kronos 2310' was added. This mixture was subsequently ground to form pigment paste.
After cooling to room temperature, 15.0 parts by weight polyester resin according to Example I (dissolved in Solvesso 150TM and butyl glycol 15.0 parts by weight solid) was then mixed with 7.5 parts by weight hexamethoxy melamine (7.5 parts by weight solid) and 0.75 part by weight paratoluene sulphonic acid (Nacure 2500 M of King Industries). The final viscosity of the resin composition was between 80-130 sec. (DIN cup 4).
The resulting composition was applied with a wire 20 coater on special chromated alucoil in a coating thickness of 100 pm. The dry coat thickness was 19-23 pm after a baking cycle of 45-50 seconds at 295°C, which corresponds with a PMT of 232 0 C-241 0
C.
The properties of the resulting coating after curing are shown in Table I.
Example IV Preparation of coating composition Example III was repeated, the polyester used being the polyester obtained according to Example II. The properties of the resulting coating after curing are shown in Table I.
(10) AE 7159 Table I
S..
coating composition according III IV to example Flexibility 1 OT 0.5 T Hardness 2 HB HB Impact resistance 3 80
QUV
4 (loss of 50% gloss) measured at an angle of 200 3000 hours 1250 hours 1) The flexibility was measured via the T-bend test (ASTM-D-4145) 2) The hardness was determined via pencil hardness 3) The impact strength was determined via ASTM-D-2794-69 (reversed impact) 4) QUV was determined via ASTM-G-53.
It is evident that the polyester according to the invention results in coil coatings with good mechanical properties and a very good outdoor durability.
The flexibility has to be 0.5 T as a maximum and is preferably CT. The QUV has to be more than 1000 hours.
Comparative Example A Example III was repeated, the polyester used being a silicon-modified polyester (Uralac SQ 870-S1F2/57M; DSM Resins). The properties of the resulting coating after curing are shown in Table II.
(10) AE 7159 Table II coating composition according to comparative example A Flexibility 3T Hardness H .0 Impact resistance QUV (loss of 50% gloss) measured at an angle of 200 1000 hours a a
Claims (11)
1. A polyester for use in outdoor-durable coating systems, having a molecular weight Mn between 2,600 and 10,000, said polyester being substantially oil-free and resulting from the process comprising the steps of reacting an acid component comprising an acid and/or an acid anhydride, with a polyalcohol, wherein at least 50 mol of said acid component comprises 1,4-cyclohexane dicarboxylic acid and a hexahydrophthalic acid (anhydride).
2. A polyester according to claim 1, wherein said polyester is based on 55-100 mol 1,4-cyclohexane dicarboxylic acid and a hexahydrophthalic acid (anhydride).
3. A polyester according to claim 1 or claim 2, wherein said molecular weight is above 3000.
4. A polyester according to any one of claims 1 to 3, wherein the amount of aromatic acid units is lower than 10 mol A polyester according to claim 4, wherein the amount of aromatic acid units is substantially 0 mol
6. A polyester according to any one of claims 1 to 5, whereit said polyalcohol is neopentylglycol and/or hydroxypivalineneopentylglycol ester.
7. A polyester for use in outdoor-durable coating systems, substantially as hereinbefore described with reference to Example I or Example II.
8. A coating composition based on a polyester according to any one of claims 1 I to 7.
9. A coating composition based on a polyester, substantially as hereinbefore described with reference to Example III or Example IV.
10. A coil coating composition based on a polyester according to any one of 25 claims 1 to 7.
11. A completely or partly coated substrate, having as coating material a coating according to any one of claims 8 to S" 12. A process for preparing a polyester for use in outdoor-durable coating systems, substantially as hereinbebore described with reference to Example I or II.
13. A method for preparing a coating composition based on a polyester, substantially as hereinbefore described with reference to Example III or IV. Dated 16 February, 1994 S" DSM N.V. Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON N:1BR)00271:KEH 9 of 2 Polyesters Suitable for Use in Outdoor-Durable Cnating Systems AE 7159 ABSTRACT The invention relates to polyesters for use in outdoor-durable coating systems such as, for instance, coil coating systems. The polyester according to the invention is based on at least 50 moles 1,4-cyclohexanedicarboxylic acid and a hexahydrophthalic acid (anhydride) as acid components. Up to a maximum of 50 moles the polyester may be based also on acid components such as, for instance, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, decanedicarboxylic acid and/or dimerized fatty acids or acid S 15 anhydrides such as, for instance, phthalic anhydride and Ssuccinic anhydride. Smo S *am oe
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL9101275A NL9101275A (en) | 1991-07-22 | 1991-07-22 | POLYESTERS APPLICABLE IN EXTREMELY DURABLE COATING SYSTEMS. |
| NL9101275 | 1991-07-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2046292A AU2046292A (en) | 1993-01-28 |
| AU649151B2 true AU649151B2 (en) | 1994-05-12 |
Family
ID=19859540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU20462/92A Ceased AU649151B2 (en) | 1991-07-22 | 1992-07-21 | Polyesters suitable for use in outdoor-durable coating systems |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5376460A (en) |
| EP (1) | EP0525871A1 (en) |
| JP (1) | JPH05239196A (en) |
| AU (1) | AU649151B2 (en) |
| CA (1) | CA2074210A1 (en) |
| FI (1) | FI923319A7 (en) |
| NL (1) | NL9101275A (en) |
| NO (1) | NO922889L (en) |
| TW (1) | TW213482B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19538061C2 (en) * | 1995-10-13 | 2001-01-04 | Basf Coatings Ag | Water-dilutable polyester |
| US6288199B1 (en) | 1999-11-02 | 2001-09-11 | Ppg Industries Ohio, Inc. | Blocked isocyanate-based compounds and compositions containing the same |
| US6284846B1 (en) | 1999-11-02 | 2001-09-04 | Ppg Industries Ohio, Inc. | Stable powder coating compositions |
| US6294619B1 (en) | 1999-11-02 | 2001-09-25 | Ppg Industries Ohio, Inc. | Stable powder coating compositions which produce consistent finishes |
| EP1487640B1 (en) * | 2002-03-04 | 2006-12-27 | Valspar Sourcing, Inc. | High-reflectivity polyester coating |
| DE102004023071A1 (en) * | 2004-05-11 | 2005-12-08 | Basf Ag | Pumpable Tricyclodecandimethylol containing composition |
| US7732506B2 (en) * | 2006-04-19 | 2010-06-08 | Stepan Company | Radiation-curable compositions for improved weather resistance |
| BRPI0810553A8 (en) * | 2007-04-27 | 2018-10-30 | Valspar Sourcing Inc | coated substrate, method for producing a coated coil, and coil coating system |
| US8389117B2 (en) * | 2008-10-30 | 2013-03-05 | Eastman Chemical Company | Hot melt adhesives for roll-applied labels |
| MX349929B (en) * | 2009-11-24 | 2017-08-21 | Stepan Co | Polyol acrylates for use in energy curable inks. |
| MX2016001306A (en) | 2013-08-02 | 2016-11-07 | Basf Se | Multilayer composition for packaging. |
| WO2019198473A1 (en) * | 2018-04-12 | 2019-10-17 | 東洋紡株式会社 | Weather resistant adhesive composition |
| WO2020149082A1 (en) | 2019-01-17 | 2020-07-23 | 東洋紡株式会社 | Copolyester and aqueous dispersion |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352924A (en) * | 1981-06-29 | 1982-10-05 | Eastman Kodak Company | Thermosetting powder coating compositions |
| JPS59131667A (en) * | 1982-09-06 | 1984-07-28 | Nippon Paint Co Ltd | Resin composition for paint containing polyester resin modified with alicyclic acid and having controlled kind of acid at terminal |
| US4535132A (en) * | 1983-12-12 | 1985-08-13 | Ppg Industries, Inc. | Thermosetting high solids solvent-based polyester polyol coating compositions |
| JPS6128562A (en) * | 1984-07-18 | 1986-02-08 | Kansai Paint Co Ltd | Thermosetting nitrogen-containing alkyd resin paint |
| JPH0224376A (en) * | 1988-07-13 | 1990-01-26 | Kansai Paint Co Ltd | Curable nitrogenous alkyd resin coating material |
| US5093752A (en) * | 1989-02-20 | 1992-03-03 | Sony Corporation | Device for moving capstan into position after tape is loaded |
-
1991
- 1991-07-22 NL NL9101275A patent/NL9101275A/en not_active Application Discontinuation
-
1992
- 1992-07-20 CA CA002074210A patent/CA2074210A1/en not_active Abandoned
- 1992-07-20 EP EP92202201A patent/EP0525871A1/en not_active Withdrawn
- 1992-07-21 JP JP4193610A patent/JPH05239196A/en active Pending
- 1992-07-21 AU AU20462/92A patent/AU649151B2/en not_active Ceased
- 1992-07-21 FI FI923319A patent/FI923319A7/en unknown
- 1992-07-21 NO NO92922889A patent/NO922889L/en unknown
- 1992-08-04 TW TW081106168A patent/TW213482B/zh active
-
1994
- 1994-03-23 US US08/216,516 patent/US5376460A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05239196A (en) | 1993-09-17 |
| NL9101275A (en) | 1993-02-16 |
| FI923319L (en) | 1993-01-23 |
| CA2074210A1 (en) | 1993-01-23 |
| AU2046292A (en) | 1993-01-28 |
| FI923319A0 (en) | 1992-07-21 |
| US5376460A (en) | 1994-12-27 |
| EP0525871A1 (en) | 1993-02-03 |
| NO922889D0 (en) | 1992-07-21 |
| FI923319A7 (en) | 1993-01-23 |
| TW213482B (en) | 1993-09-21 |
| NO922889L (en) | 1993-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9475956B2 (en) | Powder coating compositions for low temperature curing and high flow | |
| AU649151B2 (en) | Polyesters suitable for use in outdoor-durable coating systems | |
| US5326832A (en) | Powder paint and a polyester resin for powder paint | |
| EP0134691B1 (en) | Compositions curable at ambient or slightly elevated temperatures comprising a polyhxdroxy compound together with a specified epoxide/carboxylic anhydride crosslinking system | |
| USRE30102E (en) | Cross-linkable compounds based on saturated polyesters | |
| US20010036999A1 (en) | Low VOC, coating compositions having improved flexibility and impact resistance based upon nonlinear, low-molecular weight polyester polyol resins | |
| JP2515081B2 (en) | Clear-film forming liquid crosslinkable composition | |
| US5972471A (en) | Decorative coating with textured pattern | |
| JPH07508794A (en) | Method for preparing color-clear composite coatings with acid etching resistance | |
| JPS6096663A (en) | Solvent base high solid thermosettable polyester-urethane one component coating composition | |
| EP0148329A2 (en) | Thermosetting high solids solvent-based polyester-urethane two-component coating compositions | |
| US4424239A (en) | Liquid coating composition for metal surfaces, and a process for coating them with such a coating composition | |
| US4426478A (en) | Branched polyester coating compositions | |
| US4101496A (en) | Highly pigmentable, liquid coating compositions | |
| JPH0144261B2 (en) | ||
| JP3604430B2 (en) | Thermosetting and epoxide-free coating composition, method for producing the composition, powder lacquer comprising the composition, protective layer comprising the composition, and method for producing the layer | |
| US4042547A (en) | Environmentally harmless stoving lacquer systems based on alkyd resins containing condensed monohydric alcohols | |
| US4298724A (en) | Branched polyesters for adhesives and coating compositions | |
| JP4106093B2 (en) | Film-forming binder for coating composition and coating composition comprising the same | |
| US5368945A (en) | Resin composition based on a polyester resin, an amino resin and an epoxy resin | |
| AU726281B2 (en) | A Polyester resin composition, a cured resin, and a paint | |
| AU715070B2 (en) | Moisture curing coating composition | |
| CN112513194A (en) | Thermosetting coating composition for improved corrosion protection of metal substrates | |
| JP2626024B2 (en) | Coating composition and paint using the same | |
| JPH02233787A (en) | Resin composition for coating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |